Carboalkoxylation of olefins



United States Patent 3,527,794 CARBOALKOXYLATION 0F OLEFINS Richard F.Heck, McDaniel Crest, Wilmington, Del., as-

signor to Hercules Powder Company, Wilmington, Del., a corporation ofDelaware No Drawing. Filed Aug. 13, 1965, Ser. No. 479,665 Int. Cl. C07c69/54, 69/56, 69/76 U.S. Cl. 260-476 9 Claims ABSTRACT OF THE DISCLOSUREThe process involves the introduction of an organic group into anethylenically unsaturated hydrocarbon. As an example, a mixture ofcarbomethoxymercuric chloride, lithium palladium chloride and ethyleneis formed in methanol as solvent. This results in the formation of anunstable adduct between the ethylene and carbomethoxypalladium chloride.Decomposition of the adduct by maintaining it above its decompositiontemperature provides methyl acrylate as the product.

This invention relates to the preparation of substituted ethylenicallyunsaturated organic compounds by the use of organometallic compounds asintermediates.

It is known to produce saturated organic compounds by addition oforganometallic compounds to unsaturated organic compounds and subsequentremoval of the metallo group. This reaction is limited in scope by thefact that it is not applicable to many organometallic compounds-or tomany unsaturated compounds. Moreover, this reaction is applicable mostlyto highly reactive organometallic compounds which require anhydrousconditions and the absence of reactive functional groups with which sidereactions often take place.

It is an object of the present invention to produce substituted olefiniccompounds.

In accordance with the present invention, it has been found that aQ-substituted ethylenic compound is formed by producing an unstableorganometallic compound adduct of said Q-substituted ethylenic compoundand a Group VIII metal residue and decomposing said unstable adductintermediate by maintaining said intermediate above its decompositiontemperature until said decomposition is affected and that saidorganometallic compound adduct of said Q-substituted ethylenic compoundis formed as an intermediate by contacting an ethylenic compound with anorganometallic compound, in which Q is the organo group and a Group VIIImetal residue is the metallic group, or by contacting a normally stableorganometallic compound adduct of said Q-substituted ethylenic compoundand a metal residue of a metal of Groups I-A, II-A, II-B, III-A, or IV-Awith a metal salt of a Group VIII metal.

The group designations refer to the Periodic Chart of the Elements suchas is published by Fischer Scientific R ll x Q11 In these formulas the Rgroups are hydrogen or CC bonded organic radicals, other than CH Z,Where Z is halogen, OH or etherified or esterified OH. Theorganometallic compound QMX is the organometallic compound of the GroupVIII metal of the formula shown when the valence is II, and the formulais to be understood to be QM'X when the valence is III.

The organometallic compound QMX for the reaction expressed by (a) isproduced indirectly from another organometallic compound which is acompound of Q and another metal, M, by reaction with a salt of M'. Thisother organometallic compound of Q and M is a compound with acarbon-metal linkage and this organometallic compound may be in the formQM, Q M, Q M, Q4 Q Q z Q a Qz a, Qz z Qs depending on the metal M andits valence. Using QMX for an example, this reaction is expressed asfollows:

This equation expresses the reaction when both M and M' have a valenceof H and corresponding equations may be written where M and M havedifferent valences.

The organometallic compounds which undergo the reactions of thisinvention include those which have more than one carbon to metal linkageas in the case where the organo group is also an organo metallo group.More specifically, if QMX represents an organornetallic compound of thisinvention, Where Q is the organo group, M' is a Group VIII metal and Xis an anion, the Q group may be a Q'MX group. Thus, a polyorganometallic compound of this invention includes those represented bythe formula Q(M'X) where y is the number of such groups attached to Q.The number of M'X groups per molecule will most commonly be one,occasionally two, and may be 3 or more, depending on the number ofgroups which can be attached to a single Q group. For convenience indiscussion, the organometallic compounds will be referred to by theconvenient formula QMX although it is understood that the actualvalences will determine the formula in each specific case.

An organometallic compound represented by Q(M'X) will react with y molesof ethylenic compound to effect poly-substitution of the Q nucleus asfollows:

By this process, it becomes possible to introduce more than one newfunctional group into a single organic nucleus. Thus, a difunctionalaromatic compound of a Group VIII metal such as palladium can beproduced and reacted during its short life with any of a large group ofethylenic compounds to introduce two new ethylenic groups having thesame IR substituents as the original ethylenic compound. Theseorganopolymetallo compounds of Group VIII metals are produced from otherorganopolymetallo compounds as set forth above for the organomonometallocompounds as set forth above.

organometallic compounds of Q and a metal other than a Group VIII metalare well known in the art. Organometallic compounds of Group I-A metals,which are the alkali metals, are made by direct action of some compoundswith the alkali metal, e.g., malonic ester, triphenylmethane,malononitrile, benzoylacetic esters, cyanoacetic esters, and acetoaceticesters with sodium, lithium, and potassium. These may also be producedby reaction of metal alkoxides, metal alkyls or metal acetylides withthe compounds listed. In these examples, the organometallic compound ofdiethyl malonate and sodium would be NaCH(COOC H wherein the Q group isCH(COOC H Dibenzofuran reacts with ethyl sodium to produce dibenzofurandisodium in which the Q group is Cleavage of some ethers by alkali metalproduces metal alkyls useful in this invention. Methyl 2-phenyl-2-propylether, for example, reacts with potassium to form 2-phenyl-2-propylpotassium. Addition of alkali metal to some substituted ethanes producesthe organometallic compound as in the reaction of 1,l,2,2-tetraphenylethane with potassium to form diphenylmethyl potassium. Theseorganometallic compounds can be reacted with the Group VIII metalcompound in anhydrous media to form a suitable Group VIII metalorganometallic compound QMX which reacts in accordance with thisinvention with an olefin to form the Q-substituted olefin as finalproduct.

In the case of Group IIA organometallic compounds represented by theformula QMX, these are well known for Ba, Sr, Ca, Mg, Zn, Cd and Hg.These are not all equal in their properties and are handled differently.The organometallic compounds of Ba, Sr,- Ca, Mg, and Zn are highlyreactive with water and with many organic functional groups whichprecludes their use. The organometallic compounds of Cd have mildreactivity, but must be used in non-aqueous medium and are of limitedvalue. The organometallic compounds of mercury, on the other hand, donot react with water and for this reason are the most usefulorganometallic compounds of the Group II-A metals for use in thisinvention.

Organometallic compounds of Group III-A metals, such as Al, Ga, In, andT1 are useful, but those of aluminum are most practical. Organometalliccompounds of the Group III-A metals exemplified by aluminum may have theformula Q A1, Q AlX or QAlXg, and in this case the X is preferably thechloride. The preparation of organometallic compounds of these metals iswell known. The range of Q groups which can be used is somewhat limited,but Q groups such as CH phenyl and alkylated phenyl are most readilyproduced.

organometallic compounds of Group IV-A metals are those of Ge, Sn andPb. These are generally prepared from organometallic compounds of GroupI-A or Group II-A metals and the Q groups are limited only by thelimitations of reactivity of the organometallic compounds withfunctional groups that may be present in the Q group. Some of theseorganometallic compounds are water sensitive and are limited in utilityfrom that standpoint. The tin and lead organometallic compounds are ofgreatest utility of this group. The tin organometallic compounds can bein the lower or higher valence states. They are formed fromorganometallic compounds of Groups I-A or II-A and the tin chloride. Itis convenient in some cases to produce the tin organometallics from themercury organometallic, e.g., by reaction of the stannous chloride, toform the stannic organometallic compound. Methyl and phenyl tincompounds and substituted phenyl tin compounds are quite suitable forthis invention. The lead compounds are prepared similarly to the tincompounds and the organolead compounds are also readily prepared byother methods. They are less reactive with water and have advantages inthis respect for use in this invention.

The organomercury compounds are the most generally useful of the variousorganometallic compounds discussed above because of their ease ofpreparation, even in aqueous solution, and because of the variety oforganic Q groups which may be introduced thereby.

The various methods of preparation and the properties of organometalliccompounds which are useful in this invention are discussed in greatdetail in Organometallic Compounds, by G. E. Coates, Second Edition,1960, John Wiley & Sons, Inc., N.Y.

In carrying out process (a), the organometallic compound of the GroupVIII metal is produced by the reaction of a Group VIII metal salt withone of the organometallic compounds of the Group I-A, II-A, III-A orIV-A metals, and the organic Q group is transferred to the Group VIIImetal. The organometallic compound of the Group VIII metal sometimes hasa short life period at ordinary temperature and in such a case must beused promptly or be maintained at reduced temperatures well below roomtemperature of 24 C. and preferably at a temperature in the range of 20to C. until used. The usual procedure is to use the organometalliccompound promptly without purification and it can even, in mostinstances, be produced in situ in the presence of the olefinic compoundwith which it is to react.

In carrying out process (a), the adduct formed is one which may beproduced by an intermediate reaction of an organometallic compound ofthe Group I-A, II-A, III-A or IV-A metal with the olefinic compound.When process (a) is carried out in situ, there is a possibility that insome cases this intermediate may actually form. However, it appears thatthis is not always the case. Moreover, such a process is useful in thosecombinations of olefin and organometallic compound which will form thedesired adduct.

In the in situ process, wherein the organometallic compound of the GroupI-A, II-A, III-A or IV-A is normally reactive with functional groups inthe olefin in the absence of the Group VIII metal salt, the greaterreactivity with the Group VIII metal salt to form the organometalliccompound of the Group VIII metal prevents, or at least greatlydecreases, those undesired reactions which would take place in theirabsence. In this in situ process, the Group VIII metal salt is referredto hereinafter as a promoter and the Group VIII metal the promotermetal, which will be designated M.

In accordance with the preferred process of the present invention, anethylenically unsaturated compound of the formula where R is an organicsubstituent, a non-metal inorganic substituent, or hydrogen, iscontacted with (a) an organometallic compound of the formula Q (MX whereM is a metal of the group consisting of Hg, Sn, Pb, T1, and Mg, and rmand n are digits whose sum totals the valence of M, and 11 but not m maybe zero, y is a whole number from 1-5, and X is an anion, and (b) apromoter of the group consisting of salts of a Group VIII metal of thegroup consisting of Pd, Pt, Rh, Ru, Ni, and Fe and an anion, andcomplexes of said salts, as well as non-ionizing salts such asphenoxides, acetylacetonates, etc. The product of this invention is acompound of the formula o=o\ R/ Q In the above formulas of the preferredprocess,

In the above formulas of the preferred process,

R is a member of the group consisting of R R and R; R is either R or R Ris exemplified by such groups as CN, CO H, --CO metal, CO R COR CONR Ris exemplified by such groups as Cl, Br, OR F, I and --OCOCH R is' anaromatic, aliphatic, or alicyclic hydrocarbon group, which when takenalone is monovalent and when taken together with another R on the sameor adjacent carbon atom forms a hydrocarbon ring including the carbon orcarbons to which the R s are attached, is bivalent;

R is a member of the group consisting of R and H;

R is R substituted by at least one R group on any carbon except thenumber one carbon of R;

Q is exemplified by such groups as CH CH C (O OAI' (COOH) ArC O Ar,ArCOOH, --ArCHO, (CH Ar, -Ar (OH) CHO,

and Ar Ar, where Ar is a benzenoid ring radical such as phenyl,naphthyl, anthracenyl, phenanthryl, benzothienyl, fluorenyl and ringsubstitution products thereof, and y is a whole number from 1 to 5. WhenR is taken together with another R on the same or an adjacent carbon orcarbons to which the R s are attached, so as to form a hydrocarbon ring,the resulting ethylenic compound is one of a large group of organiccompounds which includes such cyclic unsaturated compounds ascyclohexene, camphene, alphapinene, beta-pinene, dicyclopentadiene,dihydrodicyclopentadiene, cyclopente'ne, benzalcyclohexane,methylidenecyclohexane, ethylidenecyclohexane, and indene. In thepresence of many of these ligands, a higher temperature may be requiredfor eifecting the elimination step of the process than in the presenceof others.

The reactions whereby the process of this invention may take place maybe expressed using divalent M and M' as follows:

Brackets are used to indicate compounds which are considered transientor too unstable to isolate. These are more stable when a compound, whichforms a coordination compound therewith, is present as is indicatedhereinafter. When all R groups are hydrogen, the product is QCI-I CHWhen two R groups are hydrogen as in the case of propylene, the productdepends on the manner in which [QM'X] adds. When Q adds to the ethyleniccarbon holding the most hydrogen, QCH=CHCH is formed and when Q adds tothe ethylenic carbon holding the least hydrogen,

is formed. In the usual case, the former appears to be favored. If thereis only one hydrogen on the ethylene carbons, only one type of additioncan lead to the elimination reaction, and it appears from the yieldsfound, that the favored mode of addition is that which leads to thesuccessful elimination reaction.

While the above theory of reaction helps to explain the process involvedand is useful for discussion purposes, it does not exclude thepossibility of ditferent intermediates and even the possibility of theformation of intermediates which can be isolated.

Furthermore, the mechanism set forth is not intended to give anindication of the order of combining the essential components of thereaction; for, QMX may be contacted with M Xg first to form the QMX andthe resultant QMX combined with the olefin, or the QMX may be contactedwith the olefin and the resultant mixture contacted with the MX or allthree components may be contacted together simultaneously. Moreover, QMXmay be formed in situ, where possible and convenient, either in thepresence of both the olefin and M'X or first in the presence of eitherone or the other of the olefin and M'X then followed by addition of theother of the two.

The process of this reaction is carried out at a temperature in therange of 0 C. to about 200' C., and the reaction may be carried outstepwise, using one temperature. for what might be considered one of thetheoretical steps and using a different temperature for what might beconsidered a subsequent step. The preferred temperature range is about15 to C. Many of the reactions are conveniently carried out at 20*50 C.

A solvent is used for convenience and the solvent used is one which doesnot compete with .the reactions taking place and in that respect arecalled inert. The solvents used need not be anhydrous in those caseswhere the organometallic compound does not decompose in water and may beany solvent which does not react with the organometallic compound. Inthis respect, consideration must be given to the fact thatorganometallic compounds of magnesium are reactive with water and manysolvents such as alcohols, ketones, esters and nitriles with whichorganomercury compounds do not react. The term inert as applied to thesolvents used is thus variable according to the organometallic compoundinvolved. While such solvents as methanol, ethanol, acetone,acetonitrile, ethyl acetate, volatile hydrocarbons such as benzene,toluene, pentane and cyclohexane, and ethers such as diethyl ether anddioxan are useful, only the hydrocarbons and ethers are inert withrespect to organomagnesium compounds, while all of them are inert to theorganomercury compounds.

The organometallic compounds include a large variety of Q groups, all ofwhich cannot be used with all of the organometallic metals M. Whilemercury is the most versatile of the organometallic metals, magnesium isone of the least versatile in this respect. Thus, when M is mercury, anyof the organo groups, Q can be used, but when M is magnesium, only theorgano groups, Q, which contain functional groups inert to theorganomagnesium compound can be used. This property of being inert isalways to be determined by the actual situation and not by theory; for

the Q group, 1-hydroxy-2,6-di-t-butyl phenyl, for example, contains anOH group which is actually inert even to organomagnesium compounds, sothat this group may function as Q in this invention with any of themetals M, while other hydroxyaryl organomctallic compounds may belimited to certain metals such as mercury.

In the process of this invention, a molar amount of both Q MX and the Msalt is required for the production of one mole of Q substitution. Thesecan be regenerated from the end products for reuse. The unstable metalsalt end product readily decomposes to liberate free metal M and thiscan be oxidatively reconverted to an M salt. There are many well knownmethods for doing this chemically, with or without electrical energy. Inthe presence of acid, for example, [MXH-MX can be converted to MX +MX atthe anode. In the presence of a redox system, [M'XH-MX can similarly beconverted to MX +MX If MXH-MX breaks down into M +MX this end productcan likewise, by either of these methods, be converted to M'X +MX FromM'X +MX in admixture, a mixture of QMX and M'X can be produced withvarying degrees of ease, the ease of so doing being greatest when M ismercury and least when M is magnesium. In many cases, QH can be reacteddirectly with MX -MX so as to obtain QMX-MX which is effective forreaction with the ethylenic compound. Moreover, this formation of QMXmay be effected in situ as will be shown hereinafter in the examples.

Since Q MX and the M' salt can both be regenerated from the end productsin situ, less than the molar amount of either may be present at the timeof reaction. From the economics standpoint, this is advantageous. It isparticularly desirable to be able to regenerate M salt whether in situor by separation of the M' end products of the reaction, regenerationoutside or within the system, and reuse of M'X salt or complex. Asindicated above, both QMX and MX can be regenerated together in certaininstances and thus much less than molar amounts of both reagents may beutilized in the system, where regeneration is practiced.

The Group VIII metal salt which is used in the process of this inventioncommonly forms complexes or coordination compounds with solvents whichare used, and this is advantageous for solubility considerations. It isadvantageous to also add inorganic salts which similarly form complexes.Lithium chloride is particularly advantageous in this respect. Organicmaterials which form coordination compounds and are useful includeacetonitrile, diand triphenyl phosphine, trimethyl phosphine, pyridine,piperidine, dipyridyl, phenanthrylene, water, arsine, triphenyl arsine,triphenyl arisine, benzonitrile, dimethyl sulfoxide, bisphosphines,phosphites, ammonia, aliphatic and aromatic amines, and even ethylene.When some of these substances which form coordination compounds with theGroup VIII metal are present, they stabilize the QMX compound as well asthe adduct and may require a higher temperature to effect theelimination step of the process.

The following examples illustrate various ramifications of thisinvention, but the invention is not to be limited thereby.

EXAMPLE 1 Into a glass pressure chamber was injected 150 ml. ethylenegas at about 25 C. and 20 ml. of a 0.1 molar solution of LiPdCl inacetonitrile was added by injection. In acetonitrile, LiPdCl appears toform rather than Li PdCl More ethylene was injected at 24 C. to apressure of 45 p.s.i.g. To the resulting solution was added withagitation 5 ml. of 0.4 molar solution of diphenylmercury in acetonitrile'by injection. After agitation for 1 hour at 24 C., a sample of theacetonitrile solution was withdrawn from the system and analyzed by gaschromatography. It analyzed 0.1 molar in styrene. This calculated to bea 62.5% yield, based on diphenylmercury used, assuming that both phenylgroups can react. However, this would be over 100%, based on palladium,unless it is assumed that the palladium is prevented from beingcompletely reduced to the metal by an oxidizing agent such as ethyleneof mercuric chloride. For instance, [PdHCl], the eliminated metalcompound can be oxidized to PdCl by giving up hydrogen to ethylene or toHgCl by the following reactions:

EXAMPLE 2 When propylene was substituted for ethylene in Example 1, theproduct was a solution of acetonitrile 0.0 molar in transpropenylbenzene and 0.015 molar 1n ClS- propenyl benzene, corresponding to ayield 56.4% of theory.

EXAMPLE 3 A mixture of 0.35 gram diphenylmercury, 1.68 grams acrolein,and 10 ml. of a 0.1 molar solution of LiPdCl in acetonitrile was stirredfor 16 hours at 24 C. A sample analyzed by gas chromatography showed theacetonitrile solution to be 0.1 molar in cinnamaldehyde. Thiscorresponds to 60% of theoretical. The cinnamaldehyde was identified asthe 2,4-dinitrophenylhydrazone, MP. 249- 250 C. (255 C. reported in theliterature).

EXAMPLE 4 A mixture of 0.35 gram diphenylmercury, 1.6 grams methyl vinylketone, and 20 ml. of 0.1 molar LiPdCl in acetonitrile was stirred 16hours at 24 C. A sample analyzed by gas chromatography showed theresulting solution to be 0.07 molar in benzalacetone. The benzalacetonewas characterized as the 2,4-dinitrophenylhydrazone, M.P. 221.5-222 C.(223 C. reported in the literature).

EXAMPLE 5 A mixture of 0.93 gram phenylmercuric chloride, 3 ml. 1.0molar solution of methyl acrylate in acetonitrile and 10 ml. 0.1 molarLiPdCl in acetonitrile was stirred 16 hours at 24 C. A sample analyzedby gas chromatography showed the resulting solution to be 0.153 molar inmethyl cinnamate. This was a of theoretical yield, based on palladium.

EXAMPLE 6 To a mixture of 32 grams anhydrous cupric chloride, 19.5 gramsmethyl acrylate, 62 grams phenylmercuric chloride, and 160 ml. methanolwas added 20 ml. of 0.1 molar Li PdCl in methanol with cooling so as tomaintain a temperature between 24 and 40 C. After 2 hours, the reactionwas complete. The solvent was removed at reduced pressure and replacedby equal parts of ether and water, and filtered to remove insolublematerial. The aqueous phase was washed with five portions of ether andall ether extracts were combined with the ether phase. The ether phase,after drying, was distilled to obtain 18.5 grams methyl cinnamate, B.P.119-137 C./ 8 mm. which crystallized readily and melted at 33 C. Thiscorresponded to 57% of theoretical yield. The purity was 99%.

EXAMPLE 7 To a mixture of 32 grams anhydrous cupric chloride, 19.5 gramsmethyl crotonate, 62 grams phenylmercuric chloride and 160 ml. methanolwas added 20 ml. of 0.1 molar Li PdCl in methanol, with cooling so as tomaintain a temperature between 24 C. and 40 C. After 24 hours at 24 C.,the solvent was distilled off in vacuo and methylene chloridesubstituted. The insoluble material was removed and the methylenechloride solution of the product was washed with water and dried. Thissolution was distilled to recover the product, B.P. -135 C./5 mm., whichweighed 10 grams. The product was fractionated by gas chromatography.The main fraction amounting to 60% of the product was shown bycarbon-hydrogen analysis and nuclear magnetic resonance spectrum to bemethyl 3-phenyl-2-butenoate. The yield of this product was 24% oftheory. It analyzed 74.53% C, 7.02% H and the NMR spectrum at 60 mo. indeuterochloroform showed: 2 singlets of relative area 3 at 142 c.p.s., asinglet of relative area 3 at 204 c.p.s., a narrow quartet of relativearea 1 at 354 c.p.s., and a multiplet of relative area at -424 c.p.s.with respect to tetramethylsilane as an external standard. These dataindicate phenyl and carbomethoxy are cis to each other.

EXAMPLE 8 To a mixture of 32 grams anhydrous cupric chloride, 18.7 gramsmethyl methacrylate, 62 grams phenylmercuric chloride and 160 ml.methanol was added 20 ml. of 0.1 molar Li PdCl in methanol, with coolingso as to maintain a temperature between 24 C. and 40 C. After 24 hours,the reaction was complete. The solvent was removed at reduced pressureand replaced by equal parts of pentane and water and filtered to removeinsoluble material. The aqueous phase was washed with five portions ofpentane ,and all pentane extracts were combined with the pentane phase.The pentane phase, after drying, was distilled to obtain 17 grams ofproduct, B.P. 108l40 C./5 mm. as a colorless liquid. This liquid wasfractionated by gas chromatography and 70% was obtained as the majorproduct. It crystallized from pentane at Dry Ice temperature ascrystals, M.P. 3637 C. This analyzed 74.46% C, 6.91% H, and was shown byinfrared to contain a carbonyl group and a CC double bond, clearlyindicating the product to be methyl 2-methyl cinnamate. The yield wasabout 35% of theory. The n.m.r. spectrum in deuterochloroform solutionat 60 m.c. had bands at '-107 c.p.s. (narrow doublet of relative area3), 209 c.p.s. (singlet of relative area 3 or 4), and at 422 c.p.s.(single relative area 5), with respect to tetramethylsilane as anexternal standard.

EXAMPLE 9 Into a pressure bottle was'introduced 0.7 gramp-(chloromercuri)anisole and propylene gas at about 24 C., with airdisplacement first at atmospheric pressure and then at 50 p.s.i.g. Then20 ml. of 0.1 molar LiPdCl in acetonitrile was introduced whilestirring. After 3 hours of agitation, a sample was analyzed by gaschromatography, which showed a 4% yield of cis-anethole and a 21% yieldof trans-anethole. v

EXAMPLE 10 In a reaction flask was placed 0.93 gram phenylmercuricchloride, 3.0 ml. of 1.0 molar methyl acrylate in acetonitrile solutionand 10 ml. of 0.1 molar LiPdCl in acetonitrile. This solution wasstirred for about 16 hours at about 24 C. and then analyzed by gaschromatography. .Analysis showed approximately 100% yield of methylcinnamate, based on the LiPdCl used.

EXAMPLE 11 A mixture of 0.21 gram of ruthenium trichloride, 0.31 gramphenylmercuric chloride, and 0.48 gram methyl acrylate in 9 ml. methanolwas heated at 45 C. for 16 hours. Gas chromatography showed at the endof that time that the resulting mixture was 0.025 molar in methylcinnamate. This is a yield of about 20% of theory.

EXAMPLE 12 A mixture of 0.26 gram of rhodium trichloride trihydrate,0.31 gram phenylmercuric chloride, and 0.48 gram methyl acrylate in 9ml. methanol was heated at 24 C. for 24 hours. Gas chromatography showedat the end of that time that the resulting mixture was 0.059 molar inmethyl cinnamate. This is a yield of about 57% of theory.

10 EXAMPLE 13 A mixture of 0.31 gram phenyhnercuric chloride, 0.22 gramferric chloride, 0.95 gram methyl acrylate and 8 ml. methanol wasstirred for 16 hours at about 24 C. Gas chromatography showed at the endof that time that the resulting mixture was 0.0084 molar in methylcinnamate. This is a yield of about 7.6% of theory.

EXAMPLE 14 A mixture of 0.21 gram diphenylrnercury, 0.22 gram nickelbromide, 0.95 gram methyl acrylate and 9 ml. acetonitrile was stirred at75 C. for 16 hours. Gas chromatography showed at the end of that timethat the resulting mixture was 0.005 molar in methyl cinnamate. This isa yield of about 5% of theory.

EXAMPLE 15 A mixture of 4.9 grams, 3,5 bis(acetoxymercuri)salicylaldehyde, 14.3 grams methyl acrylate and 160 ml. of 0.1 molarsolution of Li PdCl in methanol was stirred for 16 hours at 24 C. Thepalladium metal powder, which precipitated, was separated and thesolvent evaporated. The residue Was taken up in methylene chloride toremove insoluble salts and this solvent was evaporated. The residue was.then crystallized from absolute alcohol. There was obtained 0.274 gramof crystalline dimethyl salicylaldehyde-3,5 bis(3-acrylate), M.P.193-195 C. In chloroform solution, this compound showed an estercarbonyl absorption band at 1715 cmf an aldehyde carbonyl band at 1665cm. and a double EXAMPLE 16 In a reaction flask was placed 62 gramsphenylmercuric chloride, 19.1 grams of methyl acrylate, 20 grams ofsodium chloride, 2.0 grams cupric chloride, 120 ml. methanol and 40 ml.of 0.1 molar Li PdCl in methanol. This solution was stirred at 40 C.while passing oxygen into the solution. At 15-minute intervals, 10 ml.portions of 3 molar hydrogen chloride in methanol were added until 50ml. total had been added, and then two more portions were added one hourapart. After standing 16 hours at 24 C., the solvent was removed invacuo and the residue was diluted with water and extracted with pentane.The pentane solution, after washing with water and drying, yielded onevaporation 22.4 grams of product, boiling at 113 C./6 mm. This productanalyzed 86% methyl cinnamate (60% of theory), and 14% methyl2-methoxy-3phenylpropionate, and the two compounds were separated by gaschromatography.

EXAMPLE 17 To a mixture of 1.6 grams anhydrous cupric chloride, 2.8grams bis-(2-naphthyl)mercury, 0.84 gram acrolein, and 8 ml. methanolwas added 1 ml. of 0.1 molar Li PdCl in methanol at a temperature ofabout 24 C. After 72 hours, the reaction was considered complete. It wasdiluted with methanol and filtered. The solvent was removed at reducedpressure and the residue was converted into the2,4dinitrophenylhydrazone, M.P. 268268.5 C., weighing 0.36 gram. Thiswas 8% of theoretical yield of 3-(2-naphthyl)acrolein.

EXAMPLE 18 A mixture of 4.4 grams ferric nitrate monohydrate, 3.1 gramsdiphenylrnercury, 0.95 gram methyl acrylate, 8 ml. methanol, and 1.0 ml.0.1 molar Li PdCl in methanol was stirred 16 hours at 24 C. After thisperiod, the solution was analyzed by gas chromatography.

1 1 Analysis showed the product to be 0.327 molar in methyl cinnamate,which is a yield of 33% of theory.

EXAMPLE 19 A mixture of 1.92 grams thallium triacetate, 3.1 gramsdiphenylmercury, 0.95 gram methyl acrylate, 8 ml. methanol and 1.0 ml.0.1 molar Li PdCl in methanol was stirred 16 hours at 24 C. After thisperiod, the solution was analyzed by gas chromatography. Analysis showedthe product to be 0.364 molar in methyl cinnamate, which is a yield of36% of theory.

EXAMPLE 20* A reaction mixture of 1.81 grams 2-naphthylmercuricchloride, 4 grams acrylonitrile and 50 ml. 0.1 molar Li PdCl, inmethanol solution was stirred at 24 C. for 16 hours. The methanolsolution was filtered, diluted to incipient cloudiness with water andallowed to crystallize. Crystals M.P. 143.8-144.6 C. amounting to 0.32gram were obtained as 3 (2 naphthyl)acrylonitrile product. This amountsto 30% of theory. The 3-(2-naphthyl) acrylonitn'le is characterized byinfrared spectrum, which shows a nitrile band at 2015 cmr and a doublebond absorption at 1612 cm.- Carbon-hydrogen analysis showed 86.9% C,5.34% H.

EXAMPLE 21 A reaction mixture of 0.427 gram tetraphenyl tin, 0.95 grammethyl acrylate and ml. 0.1 molar Li PdCl in methyl alcohol was stirredat 40 C. for 3 hours. Gas chromatography showed the solution produced tobe 0.094 molar in methyl cinnamate. This corresponds to a yield of 52%of theory.

EXAMPLE 22 A reaction mixture of 3.13 grams phenylmercuric chloride,0.92 gram ethyl acrylate, 1.34 grams cupric chloride, 8 ml. 95% ethylalcohol, and 1.0 ml. 0.01 molar Li PdCl in 95% ethyl alcohol was stirredat 60 C. for 2 hours. Gas chromatography showed the solution produced tobe 0.415 molar in ethyl cinnamate. This corresponds to a yield of 42% oftheory.

EXAMPLE 23 A reaction mixture of 0.52 gram tetraphenyl lead, 0.95 grammethyl acrylate and 10 ml. 0.1 molar Li PdCl in methyl alcohol wasstirred at 24 C. for 16 hours. Gas chromatography showed the solutionproduced to be 0.164 molar in methyl cinnamate. This corresponds to ayield of 62% of theory.

EXAMPLE 24 In a reaction flask was placed 2.3 grams bis-2-naphthylmercury, 0.95 gram methyl acrylate and 100 ml. of a 0.1 molar Li PdCl inmethanol. This solution was stirred for about 16 hours at about 24 C.,filtered and then evaporated. The residue was crystallized from aqueousmethanol to obtain 0.8 gram crystalline plates, M.P. 91.6-92.2 C. Thiswas shown by carbon-hydrogen analysis (79.14% C, 5.84% H) to be methyl3-(2-naphthyl)acrylate. This is confirmed by infrared spectrum inchloroform where a carbonyl band at 1710 cm.- and a double bond at 1640cm.- appeared. The yield was 35% of theory.

EXAMPLE 25 A mixture of 17.3 grams mesitylene, 64 grams mercuricacetate, 100 ml. methanol and 1.0 ml. 70% perchloric acid was refluxedfor 1 hr. at 65 C. After cooling, 2 grams sodium acetate was added toreduce the acidity and the solution was cooled to about 80 C.Thecrystalline solids were separated, taken up in 300 ml. of chloroform.This solution was filtered and diluted with pentane to precipitate 19grams 2,4-bis(acetoxymercuri)mesitylene, M.P. 224-225 C., which analyzed60.3% Hg.

A mixture of 3.26 grams of the above 2,4-bis(acetoxymercuri)mesitylene,4.8 grams methyl acrylate and 100 ml. 0.1 molar LiPdCl in acetonitrilewas stirred 16 hours at 24 C. The reaction mixture was filtered toseparate precipitated palladium and the solvent was removed underreduced pressure. The residue crystallized from methanol diluted withwater as colorless plates, M.P. 129-129.5 C., amounting to 0.2 gram.This was shown by analysis to be dimethylmesitylene-2,4-bis(3-acrylate), the carbonhydrogen analysis being 70.5%C, 7.27% H.

EXAMPLE 26 A mixture of 3.1 grams phenylmercuric chloride, 1.62 gramsferric chloride, 0.26 gram rhodium trichloride, 0.95 gram methylacrylate and 9 ml. methanol was stirred 16 hours at 24 C. Gaschromatography on the resulting mixture showed it to be 0.318 molar inmethyl cinnamate. This was a yield of 32% of theory.

EXAMPLE 27 A mixture of 0.71 gram p-chlorornercuri-N,N-diethylaniline,0.95 grarn methyl acrylate and 20 ml. 0.1 molar Li PdCl in methanol wasstirred 16 hours at 24 C. The precipitated metal was removed and, afterremoving methanol, the residue was taken up in pentane from which methylp-diethylaminocinnamate, M.P. 41.842.2 C., crystallized out at 40 C.This product was characterized by infrared as having a carbonyl groupand a double bond. The carbon-hydrogen analysis showed 72.02% C., 8.62%H. The yield was 22% of theory.

EXAMPLE 28 A mixture of 3.2 grams mercuric acetate, 0.23 gram palladiumacetate, 8 grams acetic acid, 0.935 gram diethylaniline and 0.95 grammethyl acrylate was stirred for 16 hours at 24 C. The resulting reactionmixture was filtered, freed of solvent, taken up in pentane andcrystallized at C. to obtain 0.16 gram crude methylp-diethylaminocinnamate, M.P. 38-39 C. The yield was 14% of theory.

EXAMPLE 29 EXAMPLE 30 A mixture of 1.0 ml. 1.0 molar tetramethyl tin inmethanol, 0.95 gram methyl acrylate and 10 ml. 0.1 molar Li PdC1 inmethanol was stirred 16 hours at 25 C. Gas chromatography showed thatthe solution was 0.048 molar in methyl crotonate. This was 57% oftheoretical.

EXAMPLE 31 A mixture of 0.25 gram methyl mercuric chloride in 1 ml.methanol, 0.95 gram methyl acrylate and 10 ml. 0.1 molar Li PdCl inmethanol was stirred 24 hours at 24 C. Gas chromatography showed thatthe solution was 0.013 molar in methyl crotonate. This was 16% oftheoretical.

EXAMPLE 32 A mixture of 1.0 ml. 1.0 molar tetramethyl lead in methanol,0.95 gram methyl acrylate and 10 ml. 0.1 molar Li PdCl in methanol wasstirred 24 hours at 24 C. Gas chromatography showed that the solutionwas 0.093

molar in methyl crotonate. This was 112% of theoretical, based on onemolar of tetramethyl lead for the reaction.

EXAMPLE 33 A mixture of 1.79 grams chloromercurinitrobenzene (89%m-isomer), 4.75 grams methyl acrylate and 50 ml. 0.1 molar LizPdCL; inmethanol was stirred 3 hours at 24 C. The resulting solution wasfiltered and evaporated and the product was crystallized from aqueousmethanol to obtain 0.259 gram of needles, M.P. 121-122 C., of methylm-nitrocinnamate, the M.P. of which is reported to be 123-124 C. Theyield was 25% of theory.

EXAMPLE 34 EXAMPLE 35 j A mixture of 0.25 gram methylmercuric chloride,0.91 gram styrene and 10 ml. of 0.1 molar Li PdCl in methanol wasstirred 16 hours at 24 C. Gas chromatography showed that the solutionwas 0.068 molar in transpropenyl benzene and that the yield was 75% oftheory.

EXAMPLE 36 A mixture of 1.0 ml. of 1 molar tetramethyl tin in methanol0.91 gram styrene, and 10 ml. of 0.1 molar LigPdCL, in methanol wasstirred 16 hours at 24 C. Gas chromatography showed that the solutionwas 0.01 molar in allylbenzene and 0.136 molar in trans-polypenylbenzeneand that the yield was 95% of theoretical in the latter.

EXAMPLE 37 A mixture of 1.0 ml. of 1 molar tetramethyl lead in methanol,0.91 gram styrene and 10 ml. of 0.1 molar Li PdCl in methanol wasstirred 24 hours at 24 C. Gas chromatography showed that the solutionwas 0.192 molarin trans-polypenylbenzene and that the yeld was 108%oftheory, based on one methyl group of the tetramethyl lead reaction.

. EXAMPLE 38 A mixture of 3.94 grams p-acetoxymercuriacetanilide, 4.8grams methyl acrylate and 100 ml. 0.1 molar Li PdCl in methanol wasstirred at 24 C. for 16 hours. The reaction mixture was freed ofsolvent, dissolved in methylene chloride and chromatographed on alumina.The eluate was crystallized from methanol to obtain 0.095 gram yellowcrystals, M.P. 193194 C., the infrared spectrum of which showed acarbonyl and a double bond and an NH group. The carbon-hydrogen analysiswas 65.41% C, 6.2% H, corresponding to methyl p-acetamidocinnamate. Theyield was of theory.

EXAMPLE 39 A mixture of 3.29 grams o-chloromercuriphenol, 9.5 gramsmethyl acrylate and 100 ml. 0.1 molar Li PdCl in methanol was stirred at24 C. for 16 hours. The reaction mixture wasfreed of solvent, dissolvedin hexane and crystallized from hexane to obtain 0.061 gram colorless,crystals, M.P. 136-137 C., the infrared spectrum of which showed acarbonyl and adouble bond, corresponding to methyl o-hydroxycinnamate.The yield was 3.5% of theory.

1 4 EXAMPLE 40 A mixture of 5.5 grams mercuric oxide dissolved in 250ml. of 60% (by weight) perchloric acid and 13.0 grams o-dichlorobenzenewas stirred at 24 C. for 48 hours and poured into 1 liter of an aqueous5% sodium chloride solution. The oily product was separated, washed withwater, and dissolved in acetone from which 2.9 grams of crude3,4-dichlorophenylmercuric chloride, M.P. 206- 207 C., separated onaddition of water.

A mixture of 2.9 grams 3,4-dichlorophenylmercuric chloride, 9.5 gramsmethyl acrylate, and 100 ml. 0.1 molar Li PdCl in methanol was stirred16 hours at 24 C. The reaction mixture was filtered, concentrated underreduced pressure, and dissolved in hot hexane. From this hexane solutionat -5 C., colorless crystals, M.P. 117- 118 C., separated, amounting to0.68 gram. This cystalline product was shown by infrared to contain acarbonyl and a double bond. It analyzed 51.95% C, 3.28% H, and gave3,4-dichlorocinnamic acid on saponification and this was methyl3,4-dichlorocinnamate. Yield was 38.5% of theory.

EXAMPLE 41 A mixture of 5.5 grams mercuric oxide dissolved in 250 ml. of60% perchloric acid and 10.0 grams benzoic acid was stirred at 24 C. for16 hours and poured into a 1 liter aqueous 5% sodium chloride solution.The solid product was separated, washed with water and dissolved inacetone, from which 5.9 grams of crude m-chlorornercuribenzoic acid,M.P. 257-259 C., separated on addition of Water.

A mixture of 2.5 grams m-chloromercuribenzoic acid, 6.7 grams methylacrylate and 70 ml. 0.1 molar Li PdCl in methanol was stirred 2 hours at24 C., and then for 2 hours at C. in a closed vessel. The reactionmixture was filtered, concentrated under reduced pressure and dissolvedin hot hexane. From this hexane solution separated colorless crystals,M.P. 7980 C., amounting to 0.83 gram. This crystalline product was shownby infrared to contain a carbonyl and a double bond. It analyzed 65.17%C, 5.45% H, and gave m-carboxycinnamic acid, M.P. 274.8275.6 C., onsaponification and this was methyl m-carbomethoxycinnamate. Yield Was54% of theory.

EXAMPLE 42 A mixture of 5.5 grams mercuric oxide dissolved in 250 ml. of60% by weight perchloric acid and 10.5 grams benzaldehyde was stirredfor 3 hours at 24 C. and poured into 1 liter of 5% aqueous sodiumchloride solution to obtain 6.5 grams of m-chloromercuribenzaldehyde,M.P. 189191 C., which was dried.

A mixture of 3.41 grams m-chloromercuribenzaldehyde, 9.5 grams methylacrylate and ml. of 0.1 molar Li PdCl in methanol was stirred 16 hoursat 24 C. The reaction mixture was filtered, freed of solvent, anddissolved in hot hexane and recovered as an oil by distill ing off thehexane. The oil was methyl m-formylcinnamate, which was characterized byforming its 2,4-dinitrophenylhydrazone, M.P. 221222 C., which analyzed515.13% C, 3.81% H, 15.13% N. The yield was 3% of t eory.

EXAMPLE 43 To a mixture of 1.6 grams anhydrous cupric chloride, 3.6grams p-chloromercuribenzoic acid, 0.95 gram methyl acrylate and 8 ml.methanol was added 1.0 ml. of 0.1 molar Li PdCl in methanol at atemperature of 24 C. for 48 hours and 75 C. for 30 minutes. After thereaction was complete, the solution was filtered and the solvent wasremoved at reduced pressure, and the product was crystallized first fromhexane and then from methanol. The yield was 0.51 gram methylp-carbomethoxycinnamate, M.P. 125.8126.2 C., which analyzed 65.71% C and5.91% H and was shown by infrared to contain a carbonyl group and adouble bond. The yield was 20% of theory.

1 5 EXAMPLE 44 A mixture of 11 grams mercuric oxide dissolved in 500 ml.of 60% by weight perchloric acid and grams benzophenone was stirred for48 hours at 24 C. and poured into 2 liters of 2.5% aqueous sodiumchloride solution to obtain 4.47 grams of crude3-chloromercuribenzophenone, M.P. 251-252 C., which contained some3,3-bis(chloromercuri)benzophenone.

A mixture of 4.18 grams of this crude chloromercuribenzophenone, 9.5grams methyl acrylate and 100 ml. of 0.1 molar Li PdCl in methanol wasstirred 3 hours at 24 C. The reaction mixture was filtered, freed ofsolvent, chromatographed on alumina and recovered as an oil, whichcrystallized from methanol. The crystals, M.P. 1l3114 C., amounting to0.95 gram, were dimethyl 3,3'-benzophenone-bis(acrylate) and the yieldwas 3.5% of theory. The oil was methyl 3-benzoylphenylacrylate.

EXAMPLE 45 A mixture of 32 grams mercuric acetate, 0.0023 gram palladiumnitrate, grams benzene, and 3.8 grams methyl acrylate was heated in apressure bottle in a nitrogen atmosphere at 125 C. for 4 hours. Thereaction mixture was shown to be 0.71 molar in methyl cinnamate. This is63% of theoretical yield. The product was dissolved in pentane, freed ofinsoluble matter and distilled under reduced pressure to obtain 3.9grams methyl cinnamate, boiling at 104-107 C./ 4 mm.

EXAMPLE 46 A mixture of 0.34 gram diphenyl tin dichloride, 0.95 grammethyl acrylate and 10 ml. 0.1 molar Li PdCl in methanol was stirred at24 C. for 16 hours. The reaction mixture was shown to be 0.152 molar inmethyl cinnamate, which is 75% of theory, based on 2 moles of productfrom 1 mole of diphenyl tin dichloride.

EXAMPLE 47 To a mixture of 0.48 gram methyl acrylate and 10 ml. 0.1molar LiPdCl in acetonitrile solution, cooled to about C. and under adry nitrogen atmosphere was added 1.0 ml. of a 1.0 molar solution ofphenyl magnesium bromide in tetrahydrofuran solution. This mixture wasallowed to gradually warm up to 2 4 C. over a 16-hour period. Bychromatographic analysis, the resulting solution was shown to be 0.0067molar in methyl cinnamate. This was 8% of theory.

EXAMPLE 48 A mixture of 10 millimoles p-acetoxymercuriacetanilide and4.77 grams methyl acrylate was reacted with 100 ml. 0.1 molar Li PdCl inmethanol at 24 C. for 24 hours. From this reaction mixture was recovereda 10% of theoretical yield of methyl p-acetamidocinnamate, M.P.193.0-194.5 C.

EXAMPLE 49* A mixture of 30 millimoles p-chloromercuridiphenyl and 4.77grams methyl acrylate was reacted in 30 ml. methanol with 30 mmoles PdCland 60 mmoles LiCl at 24 C. for 16 hours. A 2% of theoretical yield ofmethyl p-phenylcinnamate, M.P. 144.5145.5 C. was isolated. Aftercrystallization further, the M.P. was 147-147.5 C.

EXAMPLE 50 A mixture of 10 millimoles of 2-naphthylmercuric chloride and3 grams allylbenzene was reacted with 110 ml. 0.1 molar Li PdCl inmethanol at 24 C. for 16 hours. The product was 1- or2-(2-naphthyl)-3-phenyll-propene, M.P. 147.6-148.0 C.

EXAMPLE 51 A mixture of 10 millimoles of 4-chloromercuri-2-nitroanisoleand 2 grams methyl acrylate was reacted with 110 ml. 0.1 molar Li PdClin methanol at 24 C. for 16 16 hours. A 17% yield of methyl3-nitro-4-methoxycinnamate, M.P. 130l30.2 C., was isolated from thereaction mixture.

EXAMPLE 52 A mixture of 10 millimoles of chloromercuribenzoic acid andabout 10 grams styrene was reacted with ml. 0.1 molar Li PDCl inmethanol at 24 C. for 16 hours. From this reaction mixture was recovereda 36% of theoretical yield of stilbene, M.P. 1592-1595 C.

EXAMPLE 5 3 A mixture of 10 millimoles 2-chloromercurinaphthalene and2.71 grams styrene was reacted with ml. 0.1 molar Li PdCl in methanol at24 C. for 16 hours. The reaction mixture was filtered, evaporated, andcrystallized from hexane. There was obtained 1.4 gramstrans-Z-naphthyl-l-phenylethylene, M.P. 157-158 C. The yield was 61% oftheory.

EXAMPLE 54 A mixture of 10 millimoles of 2-chloromercurinaphthalene and2.7 grams a-methyl styrene was reacted with 110 ml. 0.1 molar Li- PdClin methanol at 24 C. for 16 hours. The reaction mixture was filtered,evaporated, and crystallized from hexane. There was obtained 0.85 gramZ-naphthyl-l-methyl-l-phenylethylene, M.P. 108 C. The yield was 35% oftheory.

EXAMPLE 55 A mixture of 10 millimoles of chloromercuribenzene and 2.7grams propenylbenzene was reacted with 110 ml. 0.1 molar Li PdCl inmethanol at 24 C. for 16 hours. A 21% yield of 1,2-diphenylpropene, M.P.88.4-88.8 C., was isolated from the reaction mixture.

EXAMPLE 56 A mixture of 10 millimoles of phenylmercuric chloride and 3grams anethole was reacted with 110 ml. 0.1 molar Li PdCl in methanol at24 C. for 16 hours. A yield of about 20% l-p-anisyl-2-phenylpropene,melting at 186-186.4 C., was isolated from the reaction mixture.

EXAMPLE 57 A mixture of 2 grams anisole and 0.97 gram methyl acrylatewas mixed with 10 millimoles mercuric nitrate and 0.1 millimolepalladium nitrate in 7 ml. acetic acid at 24 C. for 24 hours. Analysisshowed the production of a 28% yield of methyl pmethoxycinnamate.

EXAMPLE 58 A mixture of 10 millimoles anisylmercuric chloride, 110 ml.0.1 molar Li PdCl in methanol and 2.7 grams propenylbenzene was reactedat 24 C. for 16 hours. l-phenyl-2-anisylpropene was obtained from thereaction mixture.

EXAMPLE 59 A mixture of 1.0 ml. 1.0 molar phenyltin trichloride inacetonitrile, and 10 ml. 0.1 Li PdCl in methanol was placed in a 250 ml.pressure bottle and 0.85 gram methyl acrylate was added. This wasstirred for 24 hours at 24 C. The resulting mixture yielded methylcinnamate in 77% yield.

EXAMPLE 60 A mixture of 3.5 grams bis-triphenyl phosphine palladiumdichloride (5 mmole), 1.8 grams diphenylmercury (5 mmole), 3 ml. methylacrylate and 50 ml. acetonitrile were mixed and stirred for 16 hours at24 C. The resulting product contained 2 mmoles methyl cinnamate, asshown by gas chromatography.

EXAMPLE 61 A mixture of 1 millimole phenyl mercuric cyanide, 10 ml. 0.1molar Li PdCl in methanol, and 0.98 gram methyl acrylate was stirred for24 hours at 24 C. Methyl cinnamate was obtained in 85% of theoreticalyield.

bon hydrogen analysis showed 69.34% C and 5.66% H.

EXAMPLE 63 I A mixture of 0.32 gram carbomethoxymercuric acetate, 0.91gram styrene, and ml. 0.1 molar Li PdCl in methanol solutio'n wasstirred at'24 C. for 7 2 hours. Gas chromatographic analysis showed theresulting solution to be 0.028 molar in methyl cinnamate. This is 33%of'theoretical yield.

EXAMPLE 64 A mixture of 0.3 gram carbomethoxymercuric chloride and 10ml. 0.1 molar LiPdCl in acetonitrile solution was stirred with propyleneunder p.s.i. propylene pressure at 24 C. for 72 hours. Gaschromatographic analysis showed the resulting solution to be 0.016 molarin methyl crotonate. This is 16% of theoretical yield.

EXAMPLE 65 A mixture of 0.348 gram carboethoxymercuric acetate and 10ml. 0.1 molar LiPdCl in acetonitrile solution was stirred with ethyleneunder 30 p.s.i. ethylene pressure at 24 C. for 72 hours. Gaschromatographic analysis showed the resulting solution to be 0.05 molarin ethyl acrylate. This was 50% of theoretical yield.

EXAMPLE 66 A mixture of 0.332 gram carboethoxymercuric acetate and 10ml. 0.1 molar Li PdCl in ethanol solution was stirred with 0.91 gramstyrene at 24 C. for 16 hours. Gas chromatographic analysis showed theresulting solution to be 0.013 molar in ethyl cinnamate. This is a yieldof 13% of theory.

EXAMPLE 67 A mixture of 0.295 gram carbomethoxymercuric chloride and 10ml. 0.1 molar Li2PdC14 in methanol was stirred at 24 C. for 16 hoursunder 30 p.s.i. ethylene pressure. The reaction mixture was shown to be0.050 molar in methyl acrylate, which is 50% of theory.

Examples 63-67 are directed to a particularly interestingcarboxyalkylation process wherein the organo group is a carboalkoxygroup. By reacting a carboalkoxymercury compound with an olefin in thepresence of a palladium salt, a carboxylic ester group is substitutedfor one of the ethylenic hydrogen atoms. The carboalkylation processpreferably uses mercury as the M metal and palladium as the M metal.Mercuric acetate reacts readily with carbon monoxide and an aliphaticalcohol to produce the carboalkoxymercury compound which has the formulaI] I ornoo-Hgo 6-011.

when the alcohol is methanol. Mercuric chloride does not react readilyin a similar manner but the carboalkoxymercuric acetate will react withHCl to produce carboalkoxymercuric chloride and this latter compoundwill react with olefins in the presence of PdCl in accordance with thisinvention.

In the carboalkoxylation of olefins in accordance with this invention,the olefins which undergo the reaction are the same as those broadlydescribed hereinbefore and broadly include any olefin having onehydrogen on an ethylenic carbon. The olefins which undergo the reactionare ethylene and substituted ethylenes having one unsub- 'stitutedhydrogen on the ethylenic carbon. The substituting groups, i.e., the Rgroups of may be organic and inorganic groups of all kinds. Thisincludes aliphatic, aromatic and alicyclic hydrocarbon groups and thehalo, nitro, hydroxy, carboxy, carboalkoxy, derivatives thereof. Theremay be hydroxy, ester, aldehyde, ketone, carboxylic acid, halide, nitro,or nitro, ether or amide groups in the substituted ethylene, and thesegroups may either be an R group itself or they may be substituents on anorganic R group.

The carboalkoxylation process of this invention is particularly suitablefor the production of acrylic esters, e.g., methyl acrylate fromethylene.

In the preferred carboalkoxylation process, the carboalkoxymercury salt,preferably the acetate, is prepared in the absence of ethylene, and thenthe palladium salt and ethylenic compound are added. The carrying out ofthis process in two steps is particularly desirable in the production ofacrylic esters from ethylene.

The organo group, Q, of this invention includes the wide range of organogroups which are capable of forming an organo metallic compound in whichthe organo group is joined by a carbon linkage to the metal. The termorganyl is used as a name for the organo group when used as a prefix inchemical nomenclature and the process of introducing the organyl groupinto a compound is referred to as organylation. Organylation thusincludes within its scope both alkylation and arylation.

The apparatus and reaction vessels used in this process may be ceramicglass or metal lined. Metals which may be used in the lining arestainless steel, silver, copper, or other inert metals or alloys.

The term organometallic as used herein is restricted to compounds inwhich the metal in the compound is attached by a carbon-metal linkage.

The process of this invention will thus be seen to be capable ofoperation with varying amounts of organometallic compound and a promoterand to be operable with varying ratios of organometallic compound topromoter where regeneration is practiced.

What I claim and desire to protect by Letters Patent 1s:

1. The process which comprises contacting and reacting an ethylenicallyunsaturated hydrocarbon, containing at least one hydrogen bonded to anethylenic carbon, with an organometallic compound of a Group VIII metalat a temperature in the range of 0 C. to about 200 C. to form an adductof said ethylenically unsaturated hydrocarbon and said organometalliccompound, and heating said adduct at a temperature in the same rangeuntil the product is formed, said organometallic compound being producedby reacting a salt of a Group VIII metal selected from the groupconsisting of palladium, platinum, rhodium, ruthenium, nickel and ironwith a carboalkoxy mercury, tin or lead compound.

2. The process of claim 1 in which the ethylenically unsaturatedhydrocarbon is ethylene.

3. The process ,of claim 1 in which the ethylenically unsaturatedhydrocarbon is propylene.

4. The process of claim 1 in which the ethylenically unsaturatedhydrocarbon is styrene.

5. The process of claim 1 in which the carboalkoxy mercury, tin or leadcompound is a carbomethoxy mercury compound.

6. The process of claim 1 in which the carboalkoxy mercury, tin or leadcompound is a carboethoxy mercury compound.

7. The process of claim 1 in which the Group VIII metal salt is a saltof divalent palladium.

8. The process of claim 1 in which the organometallic compound isproduced in situ under the reaction conditions of said process.

9. The process which comprises contacting and reacting ethylene with anorganometallic compound at a temperature in the range of 0 C. to about200 C. to form an adduct of ethylene and said organornetallic compoundand heating said adduct at a temperature in the same range until theproduct is produced, said organometallic compound being produced in situunder the reaction conditions of said process by reacting a salt ofdivalent palladium with carbomethoxymercuric chloride.

References Cited UNITED STATES PATENTS 3,294,830 12/1966 Horvitz et a1.260-526 X 20 OTHER REFERENCES Coates, Organo Metallic Compounds, p. 341,1960.

CHARLES B. 'PARKER, Primary Examiner D. H. TORRENCE, Assistant ExaminerU.S. Cl. X.R.

